Polarography

Polarography
Polarography is an electroanalytical technique that
involves controlled electrolysis and referred to as
“voltammetry”.
In potentimetry, potential of electrochemical cells is
measured at zero current.
In Voltammetry, a finite current is allowed to flow through
the electrochemical cells causing electrolysis.
Extent of eletrolysis may vary;
 Electrogravimetry and coloumetry involves complete
electrolysis
 Polarography and amperometry involves minute
fraction.
 Polarography
 Voltammetry techniques measure current as a
function of applied potential under conditions that
promote polarization of a working electrode.

 Polarography: Invented by J. Heyrovsky (Nobel Prize

1959). Differs from voltammetry in that it employs a
dropping mercury electrode (DME) to continuously
renew the electrode surface.

 Amperometry: Current proportional to analyte

concentration is monitored at a fixed potential.
 Polarography

Principle:
The term polarography is restricted to that voltammetric
method in which analyte, dissolved in a suitable medium, is
placed in an electrochemical cell where the electrolysis is
controlled by a variable known potential applied to the
dropping mercury electrode (DME).
 Polarography involves measurements of current-voltage
curves (polarogram), obtained when voltage is applied to
electrodes immersed in the analyte solution.
 One of the electrodes is an indicator electrode, a DME,
consists of a mercury drop hanging at the orifice of a fine
bore glass capillary.
 The capillary is connected to a mercury reservoir so that Hg
flows through the capillary at the rate of a few mg/sec.
 Polarography

 The life time of each drop is usually 3 to 5 sec. Each drop

forms a new electrode; its surface is practically unaffected
by processes taking place on the previous drop. Hence,
each drop represents a well-reproducible electrode with
fresh clean surface.
 The second electrode is a reference electrode (SCE or Ag/
AgCl); its potential remains constant during the
measurement.
 The potential at the indicator electrode varies in the
course of measurement of the current-voltage curve,
because of the change of the applied voltage.
 Polarography
 Polarography provides a limiting electrolysis current
that is proportional to the conc. of the analyte and a
half-wave potential.
 HWP is a characteristic of an individual species.
The electrolysis current results from a controlled increase
in the potential of the DME, may be represented as a
current-voltage curve called a polarogram.

A graph of current versus

potential in a polarographic
experiment is called a
polarogram.
 Polarogram

E (V vs SCE)
Typical polarogram obtained with the DME
 Components of Polarogram
The total current that flow in, consists of the following
components:
a) Residual Current, b) Migration Current and c) Diffusion Current.
a) Residual Current (ir)
The current that flows in the absence of the depolarizer (i.e. due
to the supporting electrolyte) is called residual current. This has to
be taken into consideration while interpreting the polarograms.
b) Migration Current (im)
It is the current due to migration of ions caused by the
electrostatic field between the two polarographic electrodes. The
contribution of this component is minimized by taking large
concentrations of the supporting electrolyte.
Half-wave potential: E1/2
c) Diffusion Current (id)
Diffusion current is due to electroactive substances. When the
potential of the d.m.e is in the plateau region, the
electroactive ions or molecules are reduced or oxidized as
soon as they reach the electrode surface. As a result they are
consumed and their concentration in a thin layer of solution
in contact with the electrode becomes zero.

d) Half-wave potential (E1/2)

Half wave potential, E1/2 is an important feature of a
plarogram.
It is the potential corresponding to one half the limiting
current i.e. id/2.
El/2 is a characteristic for each element and thus used for
qualitative analysis.
Apparatus
Typical electrochemical cell used in polarography

DME
Typical electrochemical cell
 Polarography

Advantage of Hg electrode
•As the Hg capillary very narrow so, able to analyse very
small volume of analyte.
•Surface of electrode is very reproducible .
•Surface area of electrode can be calculated from the
weight of drops.

Disadvantage
•Limited potential (+0.4) – (-2) V.
•Capillary is very small so easily to bloked .
 Application of Polarography
Applications:
Polarography is used widely employed for the analysis of
trace metals in the alloys, minerals/metallurgy,
environmental analysis, foodstuffs, beverages and body-
fluids, toxicology and clinical analysis.
In the biological systems it is used to determine vitamins,
alkaloids, hormones, terpenoid substances and so on.
In medical field, polarography is used to analyze natural
colouring substance of drugs and pharmaceutical
preparations, determining pesticide or herbicide residues in
food stuffs.
Since a fresh, smooth, reproducible drop is produced at
regular intervals of time contamination or surface poisoning
will be limited.
 Application of Polarography

Polarographic Analysis of Organic Compounds:

 Polarography technique is employed in organic chemistry for
I. Qualitative and quantitative analysis
To determine many organic functional groups
(Ketone, Aldehyde, Alkene, Aryl alkyne, Azomethine, Nitrile, Azo,
Azoxy, Peroxy, Disulfide, Nitro, Nitroso, Hydroxylamine, Nitrite,
Nitrate)
II. Structure determinations of organic compounds.

Polarographic Analysis of Inorganic Compounds:

i. This technique is used to determine inorganic anions and
cations.
Cations: Cu+2, Fe+3, Zn+2, etc.
Anions: Cyanide, Bromate, iodate, dichromate, etc
II. Analysis of minerals
 Application of Polarography

Pharmaceutical applications
(1) Dissolved oxygen and peroxides.
(2) Trace metals and metal-containing drugs.
(3) Antiseptics and insecticides.
(4) Vitamins.
(5) Hormones.
(6) Antibiotics.
(7) Alkaloids.
(8) Miscellaneous pharmaceutical substances.
(Acetazolamide, Hydrochlorothiazide,
nitrofurantoin)
(9) Blood serum and cancer diagnosis.
 Current in Voltammetry
 When an analyte is oxidized at the working electrode, a
current passes electrons through the external electric
circuit to the auxiliary electrode.
 This current flows from the auxiliary to the working
electrode, where reduction of the solvent or other
components of the solution matrix occurs .
 The current resulting from redox reactions at the working
and auxiliary electrodes is called a faradaic current.
 Sign Conventions:
A current due to the analyte's reduction is called a
cathodic current and, by convention, is considered
positive.
Anodic currents are due to oxidation reactions and
carry a negative value.
 Diffusion current equation: Ilkovic Equation
is a relation used in polarography relating the diffusion current (id)
and the concentration of the depolarizer (c), which is the
substance reduced or oxidized at the dropping mercury electrode.

id = k n D1/3m2/3t1/6c
Where
k is a constant which includes Faraday constant, π and the density
of mercury, and evaluated at 708 for max current and 607 for avg
current,
D is the diffusion coefficient of the depolarizer in the medium
(cm2/s),
n is the number of electrons exchanged in the electrode reaction,
m is the mass flow rate of Hg through the capillary (mg/sec)
t is the drop lifetime in seconds, and
c is depolarizer concentration in mol/cm3.
 Ilkovic Equation
Thus, id is proportional to the concentration of a certain species
under specific conditions and the above equation may be
expressed as follows:
id = kc
where
k is constant under the specific conditions.
If k is constant for a series of standard solutions of various
concentrations and an unknown, a calibration plot can be
constructed and the unknown concentration can be determined.
Clearly, the magnitude of the diffusion current depends on several
factors in addition to analyte concentration.
In quantitative polarography, it is important to control the
temperature within a few tenths of a degree.
The transport of solute to the electrode should be made to occur
only by diffusion (no stirring).
 Factors affecting the diffusion current

I. Measurement of id: This term varies with t1/6. Change in

t1/6 may cause change in id. Variation in the measurement
of id, influences Ilkovic equation and give erroneous
result.
II. Height of the mercury column (h): Both the Hg flow rate
m and the drop life t, are dependent on the dimensions
of the capillary of the DME and on the height of the
mercury column. An increase in h produces no increase
in drop size, but increases the number of drops formed
per unit of time. Relationship between m and h:
m= khcorr
where k is a constant; hcorr is the corrected h
III. Temperature: This term varies with t1/6. Change in t1/6
may cause change in id. Variation in the measurement of
id, influences Ilkovic equation and give erroneous result.
IV. Viscosity: Both the Hg flow rate m and the drop life t,
are dependent on the dimensions of the capillary of the
DME and on the height of the mercury column. An
increase in h produces no increase in drop size, but
increases the
V. Time:
 Ilkovic Equation
Significance
This equation id used in the quantitative determination
of any electroactive substance polarography, it is
important to control the temperature within a few
tenths of a degree.
The transport of solute to the electrode should be
made to occur only by diffusion (no stirring).
 Supporting electrolyte
 Current flow due to electrostatic attraction (or repulsion)
of analyte ions by the electrode is reduced to a negligible
level by the presence of a high concentration of
supporting electrolyte (1 M HCl in the Figure above).
 Increasing concentrations of electrolyte reduces the net
current, since the rate of arrival of cationic analyte at the
negative Hg surface is decreased.
 Typically, a supporting electrolyte concentration 50‑100
times greater than the analyte concentration will
reduce electrostatic transport of the analyte to a
negligible level.
 Half-wave Potential, E1/2
• Half wave potential, E1/2 is an important feature can be
derived from the plarogram.
• It is the potential corresponding to one half the limiting
current i.e. id/2.
• El/2 is a characteristic for each element and thus used for
qualitative analysis.
 Mass Transport on the Faradaic Current
There are three modes of mass transport to and from the electrode
surface: migration, convection and diffusion.
 Migration: occurs when charged particles in solution are
attracted or repelled from an electrode that has a positive or
negative surface charge. For example, a negatively charged
cathode (DME) attracts cations while repelling anions.
– This means of mass transport is undesirable in polarography.
– Migration of substance of interest is minimized by
adding a large excess of an inert substance called
‘supporting electrolyte (SE)’ to the analytical solution.
– This SE conducts almost entire current through the cell, but
does not interfere with the reaction of interest.
– The large excess of inert ions, ensures that few reactant
and product ions will move as a result of migration.
 Mass Transport Mechanisms
 Convection: This transport is operative when the solution is
agitated. This agitation is caused by density or temp
differences in various parts of electrochemical cells or it
may be produced by some mechanical stirring.
Agitation brings more electroactive substances to the
electrode surface and produces an increase in current flow.
 Diffusion: From a region of high concentration to a region of
low concentration occurs whenever the concentration of an
ion or molecule at the surface of the electrode is different
from that in bulk solution. The concentration of the
reducible species at the electrode surface is rapidly reduced
and more of this material will diffuse from the bulk of the
solution (where the conc. C is higher) toward the electrode
surface (Conc. C0 is almost depleted). Thus, a conc. gradient
C-C0 exists for the electroactive species.
 The electroactive species is frequently referred to as the
‘depolarizer’ or ‘depolarizing substance’
 This conc. gradient causes the depolarizer to move through a
diffusion layer d surrounding the polarized microelectrode.
 Each depolarizing substance has a characteristic diffusion rate
which is expressed as the diffusion co-efficient D in units of
cm2/sec.
 The limiting current iL is related to the factors which affect the
current flow during electrolysis as well as the surface area A of
the microelectrode by the following expression:

where n is the number of electrons transferred in the redox

reaction, F is Faraday's constant, D is the diffusion coefficient for
the reactant or product, CbuIk and Cx=o are the concentration of the
analyte in bulk solution and at the electrode surface, and  is the
thickness of the diffusion layer.
 Quantitative Analysis
 The principal use of polarography is in quantitative
analysis.
 Since the magnitude of the diffusion current is
proportional to the concentration of analyte, the
height of a polarographic wave tells how much
analyte is present.
 One Standard Method
• It is assumed that a linear relationship holds for the
concentration and the wave height.
• Assuming that the wave heightes for the standard
and the analyte were h1 and h2 and the
concentrations were Xstandard and Xanalyte then,

• Hstandard / hanalyte = Xstandard / Xanalyt

 Standard curves
 The most reliable, but tedious, method of quantitative
analysis is to prepare a series of known concentrations of
analyte in otherwise identical solutions.
 A polarogram of each solution is recorded, and a graph of
the diffusion current versus analyte concentration is
prepared.
 Finally, a polarogram of the unknown is recorded, using
the same conditions.
 From the measured diffusion current and the standard
curve, the concentration of analyte can be determined.
 The figure below shows an example of the linear
relationship between diffusion current and
concentration.
Standard curve for
polarographic analysis of
Al(III) in 0.2 M sodium
acetate, pH 4.7. Id is
corrected for the residual
current
 Example 1: Using a Standard Curve

Suppose that 5.00 mL of an unknown sample of Al(III) was

placed in a 100‑mL volumetric flask containing 25.00 mL of
0.8 M sodium acetate (pH 4.7) and 2.4 mM pontachrome
violet SW (a maximum suppressor). After dilution to 100
mL, an aliquot of the solution was analyzed by
polarography. The height of the polarographic wave was
1.53 µA, and the residual current‑measured at the same
potential with a similar solution containing no Al(III)‑was
0.12 µA. Find the concentration of Al(III) in the unknown.
• The corrected diffusion current is 1.53 ‑ 0.12 = 1.41
µA.
• In the figure above, 1.41 µA corresponds to [AI(III)] =
0.126 mm.
• Since the unknown was diluted by a factor of 20.0
(from 5.00 mL to 100 mL) for analysis, the original
concentration of unknown must have been
(20.0)(0.126) = 2.46 mm.
 Standard addition method
 The standard addition method is most useful when the
sample matrix is unknown or difficult to duplicate in
synthetic standard solutions.
 This method is faster but usually not as reliable as the
method employing a standard curve.
 First, a polarogram of the unknown is recorded. Then, a
small volume of concentrated solution containing a
known quantity of the analyte is added to the sample.
 With the assumption that the response is linear, the
increase in diffusion current of this new solution can be
used to estimate the amount of unknown in the original
solution.
 For greatest accuracy, several standard additions are
made.
• The diffusion current of the unknown will be
proportional to the concentration of unknown, Cx:
• ld(unknown) = kCx

• Where k is a constant of proportionality.

• Let the concentration of standard solution be C S. When
VS mL of standard solution is added to Vx mL of unknown,
• The diffusion current is the sum of diffusion currents due
to the unknown and the standard.

rearrange and solve for Cx

 Example 2: Standard Addition Calculation

 A 25.0‑mL sample of Ni2+ gave a wave height of 2.36

µA (corrected for residual current) in a polarographic
analysis.
 When 0.500 mL of solution containing 28.7 mM Ni2+
was added, the wave height increased to 3.79 µA.
Find the concentration of Ni2+ in the unknown.

 Using the above Equation we can write:

 DC Polarography
• The first voltammetric technique
(first instrument built in 1925)
• DCP measures current flowing
through the dropping mercury
electrode (DME) as a function of
applied potential
• Under the influence of gravity (or
other forces), mercury drops grow
from the end of a fine glass capillary
until they detach
• If an electroactive species is capable
of undergoing a redox process at
the DME, then an S-shaped current-
potential trace (a polarographic
wave) is usually observed
 Voltage-Time Signals in Voltammetry

• A variable potential
excitation signal is applied
to the working electrode

• Different voltammetric
techniques use different
waveforms

• Many other waveforms

are available (even FT
techniques are in use)
 Instrumentation for Voltammetry
• Sweep generators, potentiostats, cells, and data acquistion/computers
make up most systems

Basic voltammetry system suitable for undergraduate laboratory work Cyclic voltammetry cell with a
From www.edaq.com/er461.html hanging mercury drop electrode
From www.indiana.edu/~echem/cells.html
Example 1
Example 1
Example 2
Example 3
Example 4